DE1644530B - Dyes, their manufacture and use - Google Patents

Description

The invention relates to new dyes of the general formula

(SOjH) _n

¹¹ / - ^Cl

in which R is a low molecular weight alkyl group, X is a hydrogen atom or a sulfonic acid group and η is 1 or 2 and the nucleus A can otherwise be substituted by a low molecular weight alkyl group, their production and use for dyeing fibers which contain OH or NH groups .

In comparison with the known reactive dyes of the general formula (I) in which R represents a hydrogen atom, the dyes according to the invention have the advantage of tinting cannot be changed in a strongly alkaline environment. The known dyes namely form in such a Milieu a salt of the following kind.

Ar-NO ₂ S-Ar

^{N / A}

(Ar = aromatic residue)

It is therefore necessary to give the fibers an acidic treatment after dyeing and soaping to subdue to obtain the final blue shade. Make the new dyes it possible to avoid this disadvantage. On the other hand, they are more real with chlorine washing.

The dyes according to the invention can be prepared by the condensation of 2-chlorobenzothiazole sulfonic acid chloride with compounds of the general formula

O NH ₂

SO ₁ H

45

NH-R

(H)

in which X and A have the meanings given above. Accordingly, the condensation product is a mono- or disulfonated compound, which may subsequently be a Is subjected to sulfonation so as to introduce one or two additional sulfonic acid groups.

The compounds of the formula (II) can be prepared, for example, by condensation of 1-amino-4-bromoanthraquinone sulfonic acids with N, -alkyl, N, -acylphenylenediamines, then cleavage of the acyl group by hydrolysis, then optionally sulfonation . Examples of acyl groups are the acetyl, benzenesulfonyl and p-toluenesulfonyl groups. The compounds of the formula (II) can be prepared in the same way by condensing the same anthraquinone sulfonic acids with N-monoalkyldiaminobenzenesulfonic acids.

The chlorine atom is reactive in the dyes of the formula (I). It is capable of condensation to enter between the dyes and the fibers, which contain OH or NH groups. This reaction is effected by known methods, preferably in the presence of acid-binding agents Medium.

The parts and percentages given in the examples are weight units.

Example I.

4.5 parts of 1-amino ^ '- methylamino ^ -phenylamino-anthraquinone-2-sulfonic acid are dissolved in 100 parts of 1% strength aqueous sodium carbonate solution. The mixture is heated to 30 to 35 ° C. and a solution of 3.5 parts of 2-chloro-benzothiazole-sulfonic acid chloride in 15 parts of acetone is slowly added over the course of 2 hours with stirring. A 10 "strength sodium carbonate solution is added at the same time in order to keep the pH between 7 and 7.5. After 24 hours the reaction is complete and the condensation product separates out. Its separation is stopped by adding salt and filtering , dried in air and dried thereafter at 5oC under vacuum, the product is very slightly soluble in water obtained is sulfonated as follows:. IOTeile of the product are _(dissolved in 100 parts lüO "/ IGCR sulfuric acid 20 parts of 20 ° /. , Oleum / u and allowed to react at ordinary temperature until a sample is easily soluble in water (3 to 4 hours at 15 C). It is poured over ice and the dye is precipitated by adding sodium chloride, filtered, washed with a 20% sodium chloride solution, air-dried and then dried under vacuum at 50 ° C. The reactive dye obtained is a blue powder which is very easily soluble in water.

The starting material l-amino-S'-methylamino ^ -phenylamino-anthraquinone-2-sulfonic acid is produced by condensation of the sodium salt of 1-amino-4-bromo-anthraquinone-2-sulfonic acid with N-methyl-N-acetyl-m-phenylenediamine, then deacetylation by heating with an IO% sodium hydroxide solution, then acidification with hydrochloric acid.

Example 2

6 parts of the disodium salt of 1-amino-4'-methylamino-4-phenylamino-anthraquinone-2,3-disulfonic acid are dissolved in 150 parts of water. The mixture is warmed to 30 to 35 ^° C. and a solution of 3.5 parts of 2-chloro-benzothiazole-sulfonic acid chloride in 15 parts of acetone is added with stirring. A solution of 10% sodium carbonate is added at the same time in order to maintain the pH at 7 to 7.5. In the course of

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about 24 hours you fall into the reactive Dye from its solution by adding sodium chloride, filtered, air-dried and then dries at 50 C in a vacuum. The reactive dye obtained is a blue one Powder that is soluble in water.

The starting material is produced through condensation of the sodium salt of 1-amino-4-bromoanthraquinone-2-sulfonic acid with the sodium salt of I - / \ mino-4-methylamino-ben / ol-3-sulfonic acid in Variant environment at 65 to 70 C, in the presence of sodium carbonate, sodium bicarbonate and copper chloride.

Example 3

In Example I, the sodium salt / the I - Λ inino - 3 '- methylamino - 4 - phenylamino - anthraquinone-2-sulphonic acid is added by that of 1-amino-4'-methyIamino-4-phenylamino-an! hrachinon-2-sulfonic acid, in this way, after sulfonation of the condensation product, a blue dye is obtained which is more soluble than that of Example 2.

Example 4

In Example 2, 6 parts of disodium salt are replaced of l-amino-4'-methylamino-4-phenylaiTiinoanthraquinone-2,3'-disulfonic acid by 7.1 parts of the sodium salt of l-amino ^ '- methylamino-i-phcnylaniino-anthraquinone-2,5,3'-trisulfonic acid, in this way a reactive dye is obtained which, in terms of its hue, corresponds to the dye of Example 2 is similar. which, however, is very superior to the dye of Example 2 in its solubility in water.

Example 5

The procedure is as in Example 2, but with 6.5 parts of the disodium salt of l-amino-2'-methyl-3'-methylamino - 4 - phenylamino - anthraquinone - 2.5 '- disulfonic acid. You get one in the same way blue reactive acidic dye.

The starting product used in this example is prepared in the following way: The sodium salt of 1-amino-4-bromo-anthraquinone-2-sulfoiic acid is condensed in an aqueous medium in the presence of sodium carbonate and copper chloride with the sodium salt of 1-methyl-2, 6-diamino-4-benzenesulfonic acid. The mixture is left to the obtained product p-toluenesulfonic acid chloride to act, then the methylated sulfonamide with methyl sulfate in the presence of sodium hydroxide and \ erseift the N-Melhylsulfonsäurcamid by heating at KM) (in 80 ° _'0 sulfuric acid.

_s BC is ρ ie 1 6

2 parts of one of the dyes of Examples 1 to 5 are dissolved in 100 parts of water with 2 parts Sodium. One foulardierl with this solution a cotton fabric and presses the fabric into the

ίο manner from that retained by the tissue Badmenge is 75 ° / _o fabric weight equal, the m> impregnated fabric is dried, brought about 5 minutes at a temperature of 140 to 150 C ", then rinsed, treated for fifteen minutes to boiling with soap , rinsed and dried anew. Intensive blue shades of red are obtained on these Wci-o. Color-fast to light and very wash-fast until boiling. If they are subjected to a chlorine wash test, they are hardly weakened.

while those with the cntspicchendcn. not me lierlen dyes crhaltci η shades themselves after chlorine washing, convert to> irau.

This test is carried out as follows. in the Part of the dyed cotton-woe will be 45 minutes

For 2s at 83 ° C. in 50 parts of incr aqueous solution kept that per liter of 5 g of soap, 2 g of sodium carbonate and 0.1 g of active chlorine (6th ecm hypochlorite solution at 16g / l active chlorine). The tissue will flushed. 1 minute at 27 C with dilute acetic acid treated, dried and ironed with warm iron. One compares the color tones before and after the Test.

at

s ρ ι

One makes a printing pasic that does the following Components includes:

20 parts of the dye of Example 1.
100 parts urea,
20 parts of sodium carbonate,
500 parts thickener based on

Sodium alginate,
360 parts of water.

This is printed on a cotton wool webc Paste, dries, treated 5 to 10 minutes at KX) to 102 C with steam, then rinses and treated with soap until boiling. A blue tint is obtained, which is very real when washing, especially when washing with chlorine.

Claims (2)

Patent claims: I. Dyes of the general formula C-Cl N ' in which R is a low molecular weight alkyl group, X is a hydrogen atom or a sulfonic acid group and η is I or 2 and the nucleus A is otherwise substituted by a low molecular weight alkyl group can be. 2. Process / to produce color bsi open to the general formula JSO ₃ H). in which R is a low molecular alk>! group. X is a hydrogen atom or a sulfonic acid group and η I or 2 and the nucleus A can otherwise be substituted by a low molecular weight alkyl group , characterized in that 2-chloro-bcn / othiaolsulfonic acid chloride is used with a compound of the general formula condensed, in which X and A have the meanings given in claim I and optionally subsequently sulfonated the condensation product. .V Use of the l-'arhstoflc according to claim I for dyeing fibers which contain OH or NH Ciruppcn.